London Dispersion Effects on the Structure and Properties of Nonlinear Optical BiB 3 O 6 Crystal.

α-BiB 3 O 6 (BiBO) is an important nonlinear optical (NLO) material with high efficiency for applications in harmonic generations and quantum technology. Owing to its low symmetry and cooperative Bi 3+ lone pair arrangement, it has also exceptional large piezoelectric and electro-optic coefficients and strong anisotropies on other material characteristics. Previous theoretical calculations on its physical (mainly optical) properties often gave confusing results. It is found here that London dispersion (LD) tends to stabilize structures with closer pack entities like lone pair heavy ion Bi 3+ with large polarizabilities, which is ignored in most previous density functional theory (DFT) calculations. Present study shows that without considering the LD effect, the structure of α-BiB 3 O 6 (BiBO) was predicted with an over-estimated (by over 10 %) unique b-axis while underestimates a and overestimates c in a less amount. Consequently it is not possible to use the calculated structure to obtain meaningful properties of this important material. By applying a modified post-DFT LD correction based on linear combination of atomic orbitals (LCAO) and B3LYP functional, the experimental structure is well reproduced with the theoretical optimized one. Many important material property tensors of BiBO crystal are calculated in unprecedented precisions, including: dielectric constants (static and in THz range), elastic and elasto-optic constants, piezoelectric constants, refractive indices, NLO and electro-optic (EO) coefficients. Among them, theoretical calculation of the refractive indices in the THz range by diagonalizing the clamped-ion dielectric constants was firstly achieved at least for BiBO crystal. The calculation also confirms that BiBO has an exceptional large piezoelectric constant d 22 =40 pC/N and largest free EO coefficients γ 12 T ${{\gamma }_{12}^{T}}$ , γ 22 T ${{\gamma }_{22}^{T}}$ , γ 32 T ${{\gamma }_{32}^{T}}$ on the order of 10 pm/V among borate crystals. The calculation also reveals that the large free EO coefficients are largely originated from the piezoelectric induced photo-elastic effect and for practical high speed applications only the clamped-ion EO coefficients take effect. The clamped ion EO coefficient of γ 53 S ${{\gamma }_{53}^{S}}$ =-4.17 pm/V, γ b 1 S ${{\gamma }_{{\rm b}1}^{S}}$ =-2.61 pm/V are obtained for the first time and may be consulted if one seeks to design BiBO crystal as a high-speed EO modulator. Furthermore, full tensor matrix of the elasto-optic constants was obtained on the first time. Together with the calculated elastic constants, it can help to design acoustic optic modulating devices with preferable figure of merits 10 times that of traditional quartz crystal.